Improved petroleum product and art of wood preservation



Patented Aug. 23, 1932 UNITE STATES PATENT oFFicE WILLIAM H. HAMPTONAND Bianca B. rannnvs'ron, or BERKELEY, cn'nrronnm, s-

SIGNOBS, BY ,MESNE assrenmnnrs, TO STANDARD on. COMPANY or CALIFORNIA, or SAN rnanorsco, CALIFORNIA, A oonronerron or DELAWARE IMrRovEn PETROLEUM rnonuor Ann ART. or WOOD PRESERVATION :1 Drawing; Application filed December 19, 1923,

This invention relates to the preparation .of anew petroleum product and particularly to the art of timber preservatives and has to .doespecially with the preservation of piling andothertimbers from the attack of marine insects and Teredos and from fungi or other wood-destroying.organisms.

-An object of the present inventionis to produce a novelacid-sulfur oil or oils from petroleum. p

,A-n object ofjthis iinventionis to prepare from a petroleum oil, "or from products derived therefrom, a timber preservative which shall have properties, including toxicity and impregnation of wood, substantially equivalent to .those of the'well-known and widely used timber preservative calledcreosote. I Another .object' is to prepare such a timber preservative at aicost, sufficiently low that .i-tsmanufa'cture will be commercially and economically feasible.

Heretofore, when petroleum oils or products therefromhave been used for the preservation of timbers, theyhave been used ei- 325 theras paints, water-proofing agents andthe like, or they have {been used as carrier, agents .or diluents for "preservatives, the poisonous and antiseptic agents of which having been derived from some other source.

We have ---.disc0v.er.ed that both the toxic agentand the carrier agent or diluent, can be prepared from petroleum products, whereby a timber preservative is obtained having a toxicity, as well as other desirable propenties,.-substantially equivalent to those of creosote. f

In addition to the naphthenic acids which occur in some petroleum oils, for example, Russian oils, California oils, etc. there exist in petroleum oils other and more complex organic compounds of an acid sulfur character whose nature is not well under stood and which vary-both in different petroleum oils and in the distillates derived there from. i a V These compounds we herein term acid sulfuroils. These acidsulfur oils we employ as the toxic agent for our timber pre servative. i r

The timberpreservative which-this invencurring in petroleum oils.

solution'may be applied to timbers in the Serial No. 681,470. iRen-ewed November 26, 1929'.

.tion com-prises, is made up of substantially 5% or more of these acid sulfur oils mixed with approximately 95% or less of a carrier agent or diluent, which carrier agent may be anyordinary fuel oil or petroleum distillate. A fuel oil which will give a resulting mixture, having the same viscosity. as "creos0te, is preferable, though not necessary. We prefer to make-use-of a group of acid sulfur oils which occur in petroleum dis.- tillates-which have been obtained from a pressure distillation or cracking operation. The acid sulfuroils obtained from such distillates respond to several chemical reactions which, instead of being characteristic of the 265 .acid oils naturally .occurri-ng'in petroleum, are typical of phenolic bodies. Such acid sulfur oil's possess toxic properties to a somewhat greater degree than those naturally oc- These acid sulfur oilsl-have a decided toxic property toward fungi and wood-destroying organisms in general. A solution .ofthese acidsulfur oils in-a carrier or d luent comprising an ordinary fuel oil or petroleum distillate forms an effective timber .preservative having substantially all off the properties which are desirable and elf 'cti-v'e as a timber preservative in creosote. This same manner as creosote. No bleeding or exudation from the wood occursand after being processed with this solution, the wood is immediately available for service.

The following is given as an example of a preferred process by which wev extract these acid sulfur oils and employ them for the preparation of a timber preservative. To a petroleum distillate, which has been obtained from. a pressure distillation or cracking operation, we add a suflicient quantity of lye to neutralize the acid sulfur sired strength. Approximately 15% of the product obtained after the washing with Water will, when mixed with approximately- 85% offuel'oil, result in a preservative having substantially of the toxic acid sulfur oils, the balance 'beingcarrier oil. Amixture' of such proportions has been found to approximate veryclosely all the desirable and efiective properties of creosote. Other mixtures in which theme is more or less of the toxic acid sulfur oils may of course be used.

In theprocedure as outlined above, a portion of'the total quantity of fuel oil used is added to the'lye sludge before the same is neutralized with sulphuric acid. This is done to prevent the acid sulfur oil from holding up a largequantity of water, which it would do otherwise, and to minimize any loss due to the slight solubility of the acid sulfur oils inwater. The addition of a part of the carrier oil, at this; point, is however, optional. Obviously'the addition of all the carrier oil used may, if desired, be made when the final mixing to the desired strength of-toxic ingredient takes place. 7 i y e By employingadistillate obtained from a pressure distillation operation, we may util- 7 acid sulfur oils for our timber preservative.

im a waste product which sometimes results from the treatment of such a distillate. In

the treatment-of adistillate obtained from a pressure distillation operation'it issometimes' customary to employ a preliminary lye treat inent prior to the sulphuric acid treatment of the distillate; When such lye treatment is :used, the resulting lye sludge is a waste product and a great nuisance about a refinery. This waste product we use as a source of the It will therefore be seen that when such waste produced'is-employed the raw material cost for ourtoxic ingredient is very small and we are able to manufacture a timber preservative at a greatly reduced price. 1

Having'thus described our invention,jW-e claim: T V I '1. A'process of preparing a wood preservative containing a toxic compound derived from the distillatesof a pyrogenetic process of cracking petroleum oils, which comprises adding sufiicient lye solution to neutralize the acid sulfur compounds of such distillate,

removing the lye sludge, adding mineraloil to said lye sludge, neutralizing the lye sludge with a mineral acid, thereby leaving the acid sulfur compounds in the mineral oiland in a phase separate from the aqueous acid phase, and separating the oil phase from the acid phase. g V

' 2. A process of preparing a wood preservative containing toxic compounds produced from products of pressure distillation or cracking of petroleum oils, which comprises adding a lye solution to neutralize and separate the acid sulfur compounds from the products of the pressure distillation or cracking of petroleum oils, adding mineral oil to the lye sludge in proportions of'approximately 50% of the recoverable acid sulfur compounds, adding, a mineral acid adapted toneutralize the'l'ye sludge, separating the aqueous layer formed, washing the oil and acid sulfur compounds with water, and adding further-mineral oil to serve as a carrier of the toxic bodies.

3. A process of preparing a wood preservative from the products of pressure distillation or cracking of petroleum oils which comprises'adding lye solution to said products to neutralize and separate the acid'sulfur compounds, separating the lye sludge thus formed from the said "products, adding mineral oil in an amount equal to'ap'pr'oxi mately 50% of the recoverable acid sulfur compounds, adding a solution of a mineral acid to neutralize the lye present, withdrawing the resultant aqueous layer from'the'fresultant oiland acid sulfur compound layer, washing said latter layer with water, and

compounds, such toxic compounds being,

those derived fromthe distillates of a'pyrogenetic process of cracking petroleum oils when said distillates are treated with-sufficient lye solution to neutralize the acid sulfur compounds thereof and the resulting lye sludge is neutralized in the presence ofa mineral oil with a mineral acid," the toxic compounds being the resultant acid sulfur compounds which remain in the mineral oil, the wood preservative containing also a car'- rler.

5. A wood preservative consisting of acid sulfur toxic compounds, suchas are derived when a distillate of a pyrogenetic process of cracking petroleum oils is treated with sufficient lye solution to neutralize and separate the acid sulfur compounds from theproducts of pressure distillation, and mineral oil isadded to the resultant lye sludge in proportions of approximately 50% of the recoverable acid sulfur compounds in the presence of a mineral acid sufficient to neutralize treating the distillates, still containing phenolic-like acid sulphur compounds, with lye solution to neutralize the acid sulfur compounds, separating the lye sludge produced, neutralizing the lye sludge with acid and separating the aqueous layer from the resultant acid sulfur compounds.

7. An acid sulfur oil similar to thiophenols and thiotenols, the same being derived from the distillates of a pyrogenetic process of cracking petroleum oilQcontaining phenolic-like acid sulphur compounds,rwhen' said distill-ates are treated with sufficient lye solution to neutralize the acid sulfur com- 7 pounds thereof and the resulting sludge is neutralized in the presence of a mineral oil with a mineral acid, the acid sulfur oils being the resultant compound which remained in the mineral oil.

Signed at Richmond, California, day of December, 1923.

WILLIAM H. HAMPTON. v

BRUCE B. FARRINGTON.

this 11th 

